Monazo dyes from disulfonaphthyl pyrazolones and o-aminohydroxybenzenes



nucleus,

Patented Oct. 16, 1928.

UNITED. STATES. PATENT OFFICE.

LEONW. GELLER, or HAMBURG, NEW Yoizx, AssmNon ro NATIONAL ANILINE a CHEMICAL-00,, INQ, or NEW 2on3, N. Y., A CORPORATION or NEW YORK.

noNizo mrns mom DISULFONAPHTHYL PYRAZOLONES BENZENES.

No Drawing.

This invention relates tot-he manufacture and production of new monazo dyestuifs of the 'pyrazoloneseries which are of value fordyeing wool and other material, and for the production of useful lakes and pigments.

The product obtained by treating material, as by dyeing, printing or painting, with one or more of the new dyestuffs, or a lake or pigment thereof, constitutes a part of the present invention.

The new monazo dyestuffs can be prepared by coupling a. diazotized ortho-aminophenol body, or a homologue or a nuclear substitution product thereof, and which contains an acid group, i. e., a carboxyl or a sulfonic acid group, or both, as asubstituent in the benzene with a 1-(4.8-disulfo-2-naphthyl) -5-pyrazolone body. 7

.The'new dyestuifs in the free state correspond with the formula:

SOaH

wherein R signifies a methyl or a'carboxyl group and R represents a carboxylated and/or a sulfonated aryl radical of the benyellow to red to brown shades which change on after-chroinin to yellow-red to blue-red.

tints, Upon reduction, for example with naphthyl)-4-amino-5-pyrazolone body and a carboxylated and/or sulfonated Q-aminb-lhydroxy-aryl body of thebenzene series.

In producing the azo dyestuffs of the present invention, one ,molecular proportion of the dime compound of the ortho-aminohy- .droxyaryl body of the ,1 benzene series, and

which carries an acid group in the benzene nucleus, is added to a well stirred solution of the 1- (4f.8'-disulfo-2-naphthyl) -5-pyrazolone body (in slight excess of one molecular proportion) which is rendered and kept alkaline throughout the combination. 'When the coupling is complete, the mlxture 1S AND o-mrNonirDnoxY- Application filed December 23, 1925. Serial No. 77,377.

heated to 4090 C. and the dyestufi isolated ther illustrate the invention, but it will be understood that the invention is not limited thereto; The parts are by weight.

Emample.-18.9 parts .of 2-aminophenoli-sulfonic acid is dissolved in 600 parts water and 1.3 parts of 30 percenthydrochloric acid and diazotized at a temperature of about 010 C. in theusual manner with about 7 parts of sodium nitrite. The diazo solution thus obtained is introduced into a well-stirred solution of 45 parts of the sodium salt of 1- (4:.8-disulfo-2-naphthyl) -3-methyl-.5-pyrazolone dissolved in about 500 partswater containing sufficient quantity of sodium carbonate to mantain an alkaline reaction throughout the combination. During the combination, the temperature is kept at about O-10 C. The mixture is stirred for several hours, and when the combination is complete, the solution is heated to about 70 Q. and the dyestufi' precipitated by the addit1on of common salt, filtered off, pressed and dried.- Y

The new dyestuff thus obtained corre-' sponds in the 'free state with the probable formula and in the form of its sodium salt constitutes a yellowish-brown powder soluble in water with a yellowish orange color, and dyes wool in an acid bath a yellowishorange shade which is changed by after-chroming to a reddish orange tint of excellent fastness to light and to washing. Upon reduction, it yields 1 (4.8 disulfo 2 -naphthyl) -3-methyl-4- amino-5-pyrazolone and 2-amino-plienoil-4- sulfonic acid.

In a similar manner, other monazo dye-.

"orthoaminophenol bodies, their homologues and nuclear substitution products, and which carry an acid group as a substituent in the benzene nucleus, such as, for example, 2-aminophenoll -carboxylic .acid to form a dye which has the formula Hols OH I N-o-om N l 1 v oo-ou-N-N 03H 2-aminophenol-(i-ca-rboxylic acid, .Z-aniinophenol--sulfonic acid, 2-am inophenol-4- sulfo-6-carboxy'lic acid to produce I HO|S Y OH COOH N= c-oH,

CO-(IJH,N=N

OaH

0111 v 4-nitro-2-aminophen01-6-sulonic acid, 4- nitro-Q-aminophenol-G-Carboxylic 3.616., 6-

1 nitro-2-aminophenol-4-sulfonic acid, (i-chlor- 2,-aminophenol-4-sulfonic acid to form Hols on C1 N N 0-011; j

' CO-(IJHN=N SOsH 4-chlor-2-aminophenol-(i-sulfonic acid, 3-amino-2-cresol-5-sulfonic acid, 3-amino-4-cresol-5-sulfonic acid, 3-amino-4-cresol-6-sulfonic'acid to obtain diazotized ortho-aminohydroxyaryl body of the benzene series which carries an and group in the benzene nucleus with .a 1- (4f.8'- I said dyestuflfs in the group and B 'group and nucleus, the hydroxyl position to the azo bridge.

ed in the-present inventlon carry a. "methyl claim 2.

Q 5 pyrazolone body;

I free state corresponding with the probable formula:

Hols

disulfo-flf-naphthyl) som wherein R signifies a methyl or a carboxyl the benezene series which carries an acld a hydroxyl group'in the benzene group being in ortho 2. As new products, the monazo pyrazolone dyestufls obtainable by combinin a diazorepresents an aryl radical of tized ortho-aminophenol/ bOdYWlllCh carries a sulfcr-group as a substituent in the benzene nucleus with a 1-'(4'.8-disulfo-2-naphthyl) 5-pyrazolone body; said dyestufis in the free state corresponding with the probable for mula:

wherein R -signifies a methyl om carboxyl groupc'and R represents a nucleus of the benzene series which carries a sul fo-group and a hydroxyl group,

3. As a new product, the monazo pyrazo- N-C-CH:

l Adm 'SOIH g Y 4. Material treated with a 'dyestufi of claiml.

5.-Material dyed with the dyestufi of 6. Material dyed with the dy'estufi of claim 3.

the hydroxyl group being in the ortho position to the azo bridge.

lone dyestufli which in the free state correv sponds with the probableformula:

In testimony whereof I aflix my signature. I

EON WI GELLER; 

